Green azodyestuffs



Patented Get. 13, 1936 2,052,555 ra'rnr 'oFrieE GREEN AZODYE STUFFS Konrad Stenger and Carl Erich Miiller,Frank fort-on-the-Main, Germany, assignors to General Aniline Works, 1110., New York, N. Y., a corporation of Delaware No Drawing. Application May 20, 1032, Serial No. 612,633. In GermanyMay 26, 1931 10 Claims.

The present invention relates to new green azodyestuffs which can be produced on fibrous materials made of cellulose esters and ethers and to the dyed materials, more particularly it relates to azedyestuffs which can be obtained by dyeing the saidfibrous materials with a water-insoluble para-amino-mono azodyestufi, free from sulfonic and carboxylicacid groups, of the general formula: i

wherein R and R1 represent radicals of the benzene series, the radical B being at least once substituted by an alkoxy group, and the Xs represent lower saturated alkyl, cyclohexyl or benzyl radicals or jointly with the nitrogen atom represent the morpholine radical diazotizing the amino- 1 mono-azodyestuff on the fiber and developing with a'coupling componet of the general formula:

Y1 OOH wherein Y stands for hydrogen and Y1 for an alkoxy or alkyl group, or Y and Y1 jointly represent a benzene nucleus attached to the naphthalene nucleus.

The dyeings thus obtained possess green shades of good fastness properties.

The new dyestuffs thus produced on cellulose esters or ethers possess the following general formula:

Y and Y1 have the to obtain a solution. In this solution 1000 grams of acetate silk are dyed while slowly heating for 4 hour at 70 C.-'75 C. After having handled the goods, in the dye bath for A; hour, 5% of sodium acetate, calculated upon the weight of the goods are advantageously added to the bath. Thereupon the material is rinsed, the dyestufi is diazotized on the iiber in the usual manner in a freshly prepared bath and the dyeing is then developed for 1 hour at 50 C. in another bath having a weak acetic acid reaction and containing 3 per cent of 6-methoxy-2,3-hydroxynaphthoic acid, calculated uponthe weight of the goods. The azodyestufi may also be used in the form of a suspension or emulsion in a soap bath or in the presence of any other dispersion medium. There is obtained a vivid green dyeing of good fastness and discharge properties. The dyestufi produced on the fiber correspondswith the following formula:

OCH;

0 H3 O H H500 COOH (2) By using in Example 1 instead of the azodyestuif mentioned therein, 4-amino-2,5-dimethoxybenzene-azo-l-diethylaminobenzene there is obtained with the same developing component a beautiful green dyeing of valuable properties. The dyestufi produced on the fiber corresponds with the following formula:

0 CH5 /C2H5 o H OH (5cm 2 5 1150 o -c 0 OH (3) Acetate silk is dyed with the azodyestufi mentioned in Example 1 and there is used as developing component 6-methyl-2,3-hydroxynaphthoic acid. There is obtained a bluish-green dyeing of good fastness properties. The dyestuff thus produced on the fiber corresponds with the following formula:

(4) A dye bath is prepared bydissolving 3 gramsv of 2,5-dimethoxy-4-aminobenzene-azo-4'- aminotetrahydronaphthalene in 30 liters of water while adding a sufiicient quantity of hydrochloric acid to obtain a solution. In this solution 1000 grams of acetate silk are dyed while slowly heating for hour at C. C. After having handled the goods in the dye bath for A; hour, 5% of sodium acetate, calculated upon the weight of the goods, arel advantageouslyadded to the bath. 'Ihereupon the material is rinsed, the dyestuff is diazotized on the fiber in the usual manner in a freshly prepared bath, and the dyeing is then developed for 1 hour at 50 C. in another bath having a weak acetic acid reaction and containing 3% of 6-methoxy-2,3-hydroxynaphthoic acid calculated upon the weight of the goods. There is obtained a beautiful green dyeing. The dyestuif produced on the fiber corresponds with the following formula:

H30- COOH (6) By using in Example 4 instead of the dyestuif mentioned therein 3 grams of Z-methoxylamino -benzene-azo- 4 amino-tetrahydronaphthalene and developing by means of fi-methoxy- 2,3-hydroxynaphthoic acid, there are obtained Russian green dyeings. The dyestuif produced on the fiber has the following formula:

(7) By using a dye bath containing 5 grams of 2,5-dimethoxy-4-aminobenzene-azo-4'-dimethylaminotetrahydronaphthalene in 30 liters of water and developing with 6-methoxy-2,3-hydroxynaphthoic acid there are obtained bluish-green dyeings. The dyestuff thus produced on the fiber corresponds with the following formula:

OCHa

(8) A dye bath is prepared by dissolving 3 grams of 3-methoxy-4-aminobenzene-azo-4-dimethylaminobenzene in 30 liters of water while adding a sufiicient quantity of hydrochloric acid to obtain a solution. In this solution 1000 grams of acetate silk are dyed while slowly heating'for hour at 70 C.-'75 C. After having handled the goods in the dye bath for hour, 5 per cent of sodium acetate, calculated upon the weight of the goods, are advantageously added to the bath. Thereupon the material is rinsed, the dyestuif is diazotized on the fiber in the usual manner in a freshly prepared bath and the dyeing is then developed for 1 hour at 50 C. in another bath having a weak acetic acid reaction and containing 3 per cent of 2,3-hydroxyanthracene carboxylic acid calculated upon the weight of the goods. There is obtained a beautiful green dyeing. The dyestuff produced on the fiber has the following formula:

| CH: -OH 00113 COOH (9) By using instead of the azodyestufi mentioned in Example 8, 3 grams of 2,5-dimethoxy-4- aminobenzene-azo-l-diethylaniline there is obtained a yellowish green dyeing.

' (10) Instead of the azodyestuffs mentioned hereinbefore, the following ones may likewise be used:

2-methoxy-4-aminobenzene-azo 4- dimethylaminobenzene of the following formula:

CH3 0 C Ha 3-methoxy-4-aminobenzeneazo 4 -N-methylcyclohexylamino-benzene of the following formula:

CHz-CH:

4-amino-2,5-dimethoxybenzene-azo 4' di n butylamino-benzene of the following formula:

OCH:

4-amino-2,5-dimethoxybenzene-azo-4'-phenylmorpholine of the following formula:

I OOH:

CHrCH:

/O GHQ-CH1 NH:-

3-methoxy-4-aminobenzene-azo 4'-dimethylamino-2'-methylbenzene of the following formula:

I l H: O C H: 0 H3 3-methoxy- 4 -aminobenzene-azo-4 -diethylamino-2'-m'ethylbenzene of the following formula:

4-amino-2,5-dimethoxybenzenazol'-dimethy1amino-2'-chlorobenzene of the following formula:

O C H3 1 CH3 0 C H3 01 4-amino-2,5-dimethoxybenzene-azo 4-dibenzylamino-benzene of the following formula:

OCHs

Y1 COOH wherein R and R1 represent radicals of the benzene series, the radical R being at least once substituted by an alkoxy group, the Xs represent lower saturated alkyl, cyclohexyl or benzyl radicals or jointly with the nitrogen atom represent the morpholine radical, Y stands for hydrogen and Y1 for an alkoxy or alkyl group or Y and Y1 jointly represent a benzene nucleus attached to the naphthalene nucleus, which dyestuffs when produced by combining the components on fibrous materials made of cellulose esters and ethers yield green dyeings of good fastness properties. '2. The green azo-dyestuffs of the general forwherein the KS stand for lower saturated alkyl radicals, R1 for a radical of the benzene series,

at least one of the Zs for an alkoxy group and the other for hydrogen, and Y1 for an alkoxy group, which dyestuffs when produced by combining the components on fibrous materials made of cellulose esters and ethers yield green dyeings of good fastness properties.

3. The green azo-dyestuff of the formula:

0 C H3 I /C H3 0 Ha O H H300 COOH which dyestuff, when produced by combining the components on acetate silk yields a vivid green dyeing of good fastness and discharge properties.

4. The green azo-dyestufi of the formula:

which dyestuff, when produced by combining the components on acetate silk yields a beautiful green dyeing of valuable properties.

5. The green azo-dyestufi of the formula:

which dyestuff, when produced by combining the components on acetate silk yields a green dyeing of good fastness properties.

6. Fibrous materials, dyed with dyestuffs claimed in claim 1.

7. Fibrous materials, dyed with dyestuffs claimed in claim 2.

8. Fibrous materials, dyed with a dyestuff claimed in claim 3.

9. Fibrous materials, dyed with a dyestuff claimed in claim 4.

10. Fibrous materials, dyed with a dyestufi claimed in claim 5.

KONRAD STENGER. CARL ERICI-I MULLER. 

